COMPOSITIONS FOR ELASTOMERIC COMPOUNDS AND TYRES FOR VEHICLES COMPRISING REVERSIBLE CROSS-LINKING AGENT

Abstract

The present invention relates to compositions for elastomeric compounds for tyres, in particular for tyre treads, comprising particular reversible cross-linking agents, tyre components and tyres for vehicle wheels which comprise them. The present elastomeric compounds, due to their particular hysteretic behaviour, allow manufacturing tyres characterised by a lower rolling resistance during moderate driving and at the same time greater resistance to tearing and road grip during sports driving.

Claims

1-21. (canceled)

22. An elastomeric composition for tyre compounds comprising: 100 phr of at least one diene elastomeric polymer, at least 0.1 phr of at least one reversible cross-linking agent of formula (I):
A-B-C (I) wherein A is at least one functional group capable of covalently binding to the elastomeric polymer, B, optionally present, is an at least divalent inert organic residue covalently bonded to A and C groups, C is at least one multidentate organic ligand capable of reversibly complexing at least one metal cation, at least 0.1 phr of at least one salt of the metal cation, at least 0.1 phr of at least one reinforcing filler, and at least 0.1 phr of the at least one vulcanising agent.

23. The composition according to claim 22, wherein in the reversible cross-linking agent of formula (I), only one A group is present, only one C ligand is present, and the B residue is present and is divalent.

24. The composition according to claim 22, wherein in the reversible cross-linking agent of formula (I), A is chosen from activated double bonds, sulphur groups, phenols, 1,3-dipole precursors, substituted pyrroles, and dienes capable of giving Diels-Alder reactions.

25. The composition according to claim 24, wherein in the reversible cross-linking agent of formula (I), A is chosen from norbornyl, metacryl, vinylether and mercapto groups.

26. The composition according to claim 22, wherein, in the reversible cross-linking agent of formula (I), B is present and is chosen from alkylene C.sub.1-C.sub.20, arylene C.sub.6-C.sub.20, alkylene-C.sub.1-C.sub.10-arylene-C.sub.6-C.sub.10, arylene-C.sub.6-C.sub.10-alkylene-C.sub.1-C.sub.10.

27. The composition according to claim 26 wherein B includes in the chain one or more heteroatoms or one or more functional groups chosen from COO, OCO, CONH, NHCO, OCONH, NHCONH, CO, NHC(NH)NH, C(S)S, SC(S).

28. The composition according to claim 22, wherein in the reversible cross-linking agent of formula (I), B is present and has a molecular weight of less than 4000 g/mol.

29. The composition according to claim 28, wherein in the reversible cross-linking agent of formula (I), B has a molecular weight of less than 1000 g/mol.

30. The composition according to claim 22, wherein, in the reversible cross-linking agent of formula (I), the multidentate organic C ligand comprises at least one mono- or polycyclic, 5- or 6-terms ring, saturated, unsaturated or aromatic, and optionally benzocondensate heterocycle, comprising at least one heteroatom chosen from N, P, S and O.

31. The composition according to claim 30, wherein the multidentate organic C ligand comprises at least one substituted or unsubstituted, and optionally benzocondensate nitrogen heterocycle chosen from pyridine, bipyridine, terpyridine, pyrazine, pyrimidine, pyridazine, imidazole, pyrrole, pyrazole, indole, 1,10-phenanthroline, quinoline, isoquinoline, triazole, tetrazole, triazine, tetrazined.

32. The composition according to claim 22, wherein in the reversible cross-linking agent of formula (I) :only one A group is present, only one C ligand is present, and the B residue is present and is divalent; the reversible cross-linking agent of formula (I), A is chosen from activated double bonds, sulphur groups, phenols, 1,3-dipole precursors, substituted pyrroles, and dienes capable of giving Diels-Alder reactions, norbornyl, metacryl, vinylether and mercapto groups; B is present and is chosen from alkylene C.sub.1-C.sub.20, arylene C.sub.6-C.sub.20, alkylene-C.sub.1-C.sub.10-arylene-C.sub.6-C.sub.10, arylene-C.sub.6-C.sub.10-alkylene-C.sub.1-C.sub.10; and the multidentate organic C ligand comprises at least one mono- or polycyclic, 5- or 6-terms ring, saturated, unsaturated or aromatic, and optionally benzocondensate, heterocycle, comprising at least one heteroatom chosen from N, P, S and O.

33. The composition according to claim 22, wherein, in the reversible cross-linking agent of formula (I), A is SH or norbornyl, B is O(CH.sub.2).sub.1-11, and C is 2,6-bis(1-methylbenzimidazol-2-yl)-pyridin-4-yl.

34. The composition according to claim 22, wherein the metal cation is chosen from alkaline earth metals (2A group), transition metals, lanthanides Cu.sup.2+, Fe.sup.2+, Zn.sup.2+, Mg.sup.2+, Ca.sup.2+, Ru.sup.3+, Tb.sup.3+ and Eu.sup.3+.

35. The composition according to claim 22, wherein the salt comprises an anion and the anion is a weakly coordinating anion a tosylate, a bistriflimidate or a triflate.

36. The composition according to claim 22, wherein the salt is zinc triflate.

37. The composition according to claim 22, wherein the at least one reversible cross-linking agent of formula (I) is present in an amount ranging from 0.5 phr to 20 phr.

38. The composition according to claim 22, wherein the at least one salt of the metal cation is present in an amount ranging from 0.2 phr to 7 phr.

39. The composition according to claim 22, wherein the molar ratio of reversible cross-linking agent (I) to the salt of the metal cation ranges from 6:1 to 0.5:1

40. The composition according to claim 22, wherein the at least one reinforcing filler is present in an amount ranging from 1 phr to 150 phr and is chosen from carbon black, white fillers, silicate fibres, derivatives thereof and mixtures thereof; and the at least one vulcanising agent is present in an amount from 0.1 phr to 10 phr and is chosen from sulphur, sulphur agents, peroxides, and mixtures thereof.

41. A vulcanised elastomeric tyre compound obtained by mixing and vulcanising the elastomeric composition according to claim 22.

42. A process for preparing the vulcanised elastomeric compound according to claim 41, comprising a first non-productive step and a second productive step, comprising in the first non-productive step, mixing at least one dienic elastomeric polymer, at least one reinforcing filler, and optionally, in whole or in part, at least one reversible cross-linking agent of formula (I) and at least one salt of the metal cation, wherein wherein the salt comprises an anion and the anion is a weakly coordinating anion a tosylate, a bistriflimidate or a triflate, to produce a first elastomeric compound, in the second productive step, adding to the first elastomeric compound at least one vulcanising agent and optionally, in whole or in part, the at least one reversible cross-linking agent of formula (I) and the at least one salt of the metal cation, and mixing the components, to produce a vulcanisable elastomeric compound, provided that the at least one reversible cross-linking agent of formula (I) and the at least one salt of the metal cation are added in at least one of the two steps, and vulcanising the vulcanisable elastomeric compound, to produce the vulcanised elastomeric compound.

43. The process according to claim 42, wherein the reversible cross-linking agent of formula (I) is added in the first non-productive step while the metal cation salt in the second productive step.

44. A tyre component comprising the elastomeric compound according to claim 41.

45. The tyre component according to claim 44, wherein the tyre component is chosen from tread band, anti-abrasive strip, and sidewall.

46. A tyre for vehicle wheels comprising at least one tyre component according to claim 44.

Description

BRIEF DESCRIPTION OF THE FIGURES

[0075] With reference to the accompanying Figures:

[0076] FIG. 1 schematically shows a semi-sectional view of a tyre for vehicle wheels according to the present invention;

[0077] FIGS. 2a and 2b show the thermal tests (TGA and DSC, respectively) carried out on a sample of the reversible cross-linking agent HS-MeBIP (I-C) (+Q heating, Q cooling);

[0078] FIGS. 3a and 3b show the UV absorption pattern during complexation studies of samples of the intermediate ligand 2 with triflate zinc, in particular the UV absorption pattern from 250 nm to 450 nm (FIG. 3a) and the UV absorption pattern at 314 nm and 341 nm, wavelengths characteristic of the absorption of the ligand and its complex, respectively, as the metal/ligand ratio (M/L) varies (FIG. 3b);

[0079] similarly FIGS. 3c and 3d show the UV absorption pattern during complexation studies of samples of the intermediate ligand 2 with zinc chloride;

[0080] similarly FIGS. 3e and 3f show the UV absorption pattern during complexation studies of samples of the intermediate ligand 2 with zinc 2-ethylhexanoate;

[0081] similarly FIGS. 3g and 3h show the UV absorption pattern during complexation studies of samples of the intermediate ligand 2 with terbium triflate;

[0082] similarly FIGS. 3i and 31 show the UV absorption pattern during complexation studies of samples of the ligand HS-MeBIP (I-C) with zinc bistriflimide [Zn(CF.sub.3SO.sub.2N).sub.2];

[0083] FIGS. 4a-4c show the module E pattern (dashed line) and of the Tan delta (solid line) in the temperature range from 20 C. to 170 C. of the vulcanised samples of compounds 1-3 respectively, measured in conditions of low deformation;

[0084] FIG. 5 shows the Tan delta pattern in the temperature range from 20 C. to 170 C. of the vulcanised samples of compounds 1-3, respectively, measured in conditions of low deformation;

[0085] FIGS. 6a-6b respectively show the module E pattern (dashed line) and of the Tan delta (solid line) in the temperature range from 70 C. to 170 C. of the vulcanised samples of compounds 1-2, respectively, measured under conditions of high deformation;

[0086] FIG. 7 shows the percentage pattern (by weight) of the cyclohexane swelling of compounds 1-3, before and after the addition of tetramethylethylenediamine TMEDA at 225 min.

DETAILED DESCRIPTION OF THE INVENTION

[0087] The elastomeric composition for tyre compounds according to the present invention is characterized by one or more of the following preferred aspects taken alone or in combination with one another.

[0088] The elastomeric composition according to the invention comprises at least 100 phr of at least one diene elastomeric polymer.

[0089] The diene elastomeric polymer (A) may be selected from those commonly used in sulphur-vulcanisable elastomeric compositions, which are particularly suitable for producing tyres, i.e. from among solid elastomeric polymers or copolymers with an unsaturated chain having a glass transition temperature (Tg) generally lower than 20 C., preferably in the range from 0 C. to -110 C.

[0090] These polymers or copolymers may be of natural origin or may be obtained by solution polymerization, emulsion polymerization or gas-phase polymerization of one or more conjugated dienes, optionally mixed with at least one comonomer, preferably selected from monoolefins, monovinylarenes and/or polar comonomers, typically in an amount not exceeding 60% by weight.

[0091] The conjugated dienes generally contain from 4 to 12, preferably from 4 to 8 carbon atoms and may be selected, for example, from the group comprising: 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 3-butyl-1,3-octadiene, 2-phenyl-1,3-butadiene and mixtures thereof. 1,3-butadiene and isoprene are particularly preferred.

[0092] The monoolefins can be selected from ethylene and -olefins generally containing from 3 to 12 carbon atoms, such as for example propylene, 1-butene, 1-pentene, 1-hexene, 1-octene or mixtures thereof.

[0093] Monovinylarenes, which may optionally be used as comonomers, generally contain from 8 to 20, preferably from 8 to 12 carbon atoms and may be selected, for example, from: styrene; 1-vinylnaphthalene; 2-vinylnaphthalene; various alkyl, cycloalkyl, aryl, alkylaryl or arylalkyl derivatives of styrene, such as, for example, -methylstyrene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4-p-tolyl-styrene, 4-(4-phenylbutyl)styrene, and mixtures thereof. Styrene is particularly preferred.

[0094] Polar comonomers that may optionally be used, can be selected, for example, from among acrylic acid and alkylacrylic acid esters, acrylonitriles, or mixtures thereof, such as, for example, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, acrylonitrile and mixtures thereof.

[0095] Preferably, the diene elastomeric polymer (A) may be selected, for example, from cis-1,4-polyisoprene (natural or synthetic, preferably natural rubber), 3,4-polyisoprene, polybutadiene (in particular polybutadiene with a high content of 1,4-cis), optionally halogenated isoprene/isobutene copolymers, 1,3-butadiene/acrylonitrile copolymers, styrene/1,3-butadiene copolymers, styrene/isoprene/1,3-butadiene copolymers, styrene/1,3-butadiene/acrylonitrile copolymers, and mixtures thereof.

[0096] The elastomeric composition may possibly comprise at least one polymer of one or more monoolefins with an olefinic comonomer or derivatives thereof. The monoolefins can be selected from: ethylene and -olefins generally containing from 3 to 12 carbon atoms, such as for example propylene, 1-butene, 1-pentene, 1-hexene, 1-octene or mixtures thereof. The following are preferred: copolymers selected from ethylene and an -olefin, optionally with a diene; isobutene homopolymers or copolymers thereof with small amounts of a diene, which are optionally at least partially halogenated. The diene possibly present generally contains from 4 to 20 carbon atoms and is preferably selected from: 1,3-butadiene, isoprene, 1,4-hexadiene, 1,4-cyclohexadiene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, vinylnorbornene or mixtures thereof. Among them, the following are particularly preferred: ethylene/propylene (EPR) copolymers or ethylene/propylene/diene (EPDM) copolymers; polyisobutene; butyl rubber; halobutyl rubbers, in particular chlorobutyl or bromobutyl rubbers; and mixtures thereof.

[0097] The above-mentioned polymers can optionally be functionalised along the main chain or at the ends thereof.

[0098] The functional group may be introduced into the elastomeric polymer by processes known in the art such as, for example, during the production of the elastomeric polymer by copolymerisation with at least one corresponding functionalised monomer containing at least one ethylene unsaturation; or by subsequent modification of the elastomeric polymer by grafting at least one functionalised monomer in the presence of a free radical initiator (for example, an organic peroxide).

[0099] Alternatively, the functionalisation may be introduced by reaction with suitable terminating agents or coupling agents. In particular, the diene elastomeric polymers obtained by anionic polymerization in the presence of an organometallic initiator (in particular, an organolithium initiator) may be functionalised by reacting the residual organometallic groups derived from the initiator with suitable terminating agents or coupling agents such as, for example, amines, amides, imines, carbodiimides, alkyltin halides, substituted benzophenones, alkoxysilanes, aryloxy silanes, alkyldithiols, alkyldithiolsilanes, carboxyalkylthiols, carboxyalkylthiolsilanes, and thioglycols.

[0100] Useful examples of terminating agents or coupling agents are known in the art and described, for example in patents EP2408626, EP2271682, EP3049447A1, EP2283046A1, EP2895515A1, EP451604, U.S. Pat. No. 4,742,124, WO2015/086039A1 and WO2017/211876A1.

[0101] Preferably, said at least one functionalised elastomeric polymer is obtained from polybutadiene (in particular polybutadiene with a high content of 1,4-cis), styrene/1,3-butadiene copolymers, styrene/isoprene/1,3-butadiene copolymers, styrene/1,3-butadiene/acrylonitrile copolymers, and mixtures thereof.

[0102] Advantageously, said at least one functionalised elastomeric polymer (b) is obtained from styrene/1,3-butadiene copolymers.

[0103] Useful examples of functionalised diene elastomeric polymers are the functionalised styrene butadiene copolymers SPRINTAN SLR 3402 e SPRINTAN SLR 4602, SPRINTAN SLR 4630, manufactured and distributed by Trinseo, PA, USA.

[0104] The elastomeric composition according to the invention may comprise two or more elastomeric polymers as defined above, in a mixture.

[0105] The elastomeric composition for tyres according to the present invention may comprise at least 0.5 phr, preferably at least 2 phr, more preferably at least 5 phr, of at least one reversible cross-linking agent of formula (I)

A-B-C (I)

[0106] The elastomeric composition for tyres according to the present invention may comprise not more than 20 phr, preferably not more than 15 phr, 10 phr or 8 phr of at least one reversible cross-linking agent of formula (I).

[0107] Preferably, the elastomeric composition for tyres according to the present invention comprises from 0.5 to 20 phr, preferably from 1 to 15 phr or from 2 to 10 phr, more preferably from 4 to 8 phr of at least one reversible cross-linking agent of formula (I).

[0108] In the reversible cross-linking agent of formula (I), A is at least one functional group capable of covalently binding to the elastomeric polymer.

[0109] A group may bind to the elastomeric polymers of the compound either directly or through the formation of sulphide bridges.

[0110] Preferably, A is a group selected from the activated double bonds, the sulphur groups such as mercapto, di- and polysulphides and thioesters, the reactive phenols having at least one unsubstituted ortho or para position, the precursors of 1,3-dipoles, such as the 2,5-disubstituted tetrazoles described for example in patent application IT102019000025804, the pyrroles substituted in the positions proximal to nitrogen as described for example in WO2020225595A1 and WO20180876851A1 and the diene groups capable of giving Diels-Alder reactions.

[0111] In one embodiment, A group is an activated double bond.

[0112] By activated double bond it is meant a double bond made reactive by conjugated electron-attracting or donor groups, by electron-rich or electron-poor atoms or by particular steric constraints such as the inclusion of the double bond in tensioned cycles.

[0113] Examples of activated double bonds are vinyls, unsaturated tensioned cyclic systems and unsaturated alpha-beta bonds, preferred examples are norbornene, methacryl and vinyl ether.

[0114] In one embodiment, A group is a sulphur group.

[0115] Examples of preferred sulphur groups capable of covalently binding to the elastomeric polymer are the SH, SS, S(S)n-S, SC(O)R, SC(S)RSNRR wherein R, R and R independently represent C.sub.1-C.sub.20alkyl, C.sub.6-C.sub.20 aryl, alkyl-C.sub.1-C.sub.10-aryl-C.sub.6-C.sub.10, aryl-C.sub.6-C.sub.10-alkyl-C.sub.1-C.sub.10, or R and R may optionally be fused in a cycle. At least one A group is present in the reversible cross-linking agent of formula (I) but two or more groups A, equal or different from each other, may be present.

[0116] In a preferred embodiment, only one A group is present in the reversible cross-linking agent of formula (I).

[0117] Typically these functional groups react with the elastomer under normal vulcanisation conditions, forming covalent bonds.

[0118] During the reaction, the A group of the reversible cross-linking agent may partially interfere with the sulphur-based vulcanising system present in the compound and bind to the elastomer through polysulphide bridges, thus consuming part of the vulcaniser and, in fact, reducing the extent of the sulphur cross-linking. In these cases, the skilled in the art will be able to suitably modify the sulphur vulcanisation package, varying amounts and components, to compensate for the possible loss in the sulphur cross-linking and restore the normal level thereof.

[0119] In the reversible cross-linking agent of formula (I) there is optionally present a B group, i.e. an at least divalent inert organic residue, covalently linked to A and C groups, which acts as a spacer.

[0120] Inert organic B residue means an organic residue that is sufficiently stable under normal conditions of processing, vulcanisation and use of the elastomeric compound.

[0121] In one embodiment, B group is absent.

[0122] An example of a reversible cross-linking agent of formula (I) is the following compound (I-A):

##STR00002##

wherein A=SH, B is absent and C=ter-pyridyl.

[0123] This compound is described in Example 3 of EP2607381A1.

[0124] In one embodiment, B group is present and is selected from alkylene C.sub.1-C.sub.20, arylene C.sub.6-C.sub.20, alkylene-C.sub.1-C.sub.10-arylene-C.sub.6-C.sub.10, arylene-C.sub.6-C.sub.10-alkylene-C.sub.1-C.sub.10, possibly including in the chain one or more heteroatoms such as N, O, S, B, P or Si or one or more functional groups such as for example COO, OCO, CONH, NHCO, OCONH, NHCONH, CO, NHC(NH)NH, C(S)S, SC(S).

[0125] Alkylene and arylene refer to an at least divalent radical obtained by removing at least one hydrogen atom from an alkyl and aryl group, respectively.

[0126] Examples of preferred divalent B groups are OCH.sub.2, O(CH.sub.2).sub.6, O(CH.sub.2).sub.10, O(CH.sub.2).sub.11, OC(O)NH(CH.sub.2).sub.6NHC(O)O, NHC(O)NH, (CH.sub.2).sub.6NHC(O). Preferably, the B group has a molecular weight lower than 2000 g/mol, more preferably lower than 1000 g/mol, even more preferably lower than 500 g/mol.

[0127] In the reversible cross-linking agent of formula (I), C is a multidentate organic ligand capable of reversibly coordinating at least one metal cation.

[0128] The multidentate organic C ligand is an at least bidentate organic ligand, preferably it is at least tridentate, more preferably it is tridentate.

[0129] The multidentate organic C ligand may be charged or neutral, preferably it is neutral.

[0130] The multidentate organic C ligand comprises at least two heteroatoms, preferably selected from N, P, S and O, more preferably at least two nitrogen atoms, capable of forming coordination bonds with the metal cation.

[0131] Preferably, the multidentate organic C ligand comprises at least two monodentate ligand residues such as for example the ligands described in Coordin. Chem. Rev. (1973), 9 (3-4), 219-274, in particular 237-246, par. E, subpar. i) and ii); Helv. Chim. Acta (1993), 76, 372-384; Coordin. Chem. Rev. (1997), 160, 1-52, in particular 18-24, par. 3.2.3; Inorg. Chem. (2009), 48, 1132-1147; Chem. Eur. J. (2016), 22, 17892-17908, in particular 17894-17901; Molecules (2020), 25(21), 4984-5008.

[0132] Preferably, the multidentate organic C ligand comprises at least one mono- or polycyclic, 5- or 6-terms ring heterocycle, saturated, unsaturated or aromatic, possibly benzocondensate, comprising at least one heteroatom selected from N, P, S and O.

[0133] Preferably, the multidentate organic C ligand comprises at least one nitrogen heterocycle selected from pyridine, bipyridine, terpyridine, pyrazine, pyrimidine, pyridazine, imidazole, pyrrole, pyrazole, indole, 1,10-phenanthroline, quinoline, isoquinoline, triazole, tetrazole, triazine, tetrazine, substituted or unsubstituted, possibly benzocondensate, more preferably, the multidentate organic C ligand comprises at least one nitrogenous heterocycle selected from pyridine and benzimidazole.

[0134] The skilled in the art, by appropriately selecting the C ligand and its substituents, is capable of modulating the coordination capacity of the ligand itself and therefore of conveniently shifting the equilibrium of the cross-linking/uncross-linking reaction as a function of the temperatures of interest for the present tyre applications.

[0135] Examples of ligands C are the compounds of formula (II), (III) and (IV) described below.

[0136] Examples of tridentate C ligand (II) are the tripyridines of formula (II-A):

##STR00003##

wherein R1 is B group, and R2 are independently selected from H and linear or branched C.sub.2-C.sub.6 alkyl.

[0137] An example of a particularly preferred tridentate C ligand (II) of the bis(benzimidazol) pyridine class is 2,6-bis(1-methylbenzimidazol-2-yl)-pyridine-4-yl (MeBIP) of formula:

##STR00004##

[0138] Examples of bidentate ligands C are the compounds of formula (III) or (IV):

##STR00005##

wherein R1 is B group, and R2 are independently selected from H and linear or branched C.sub.2-C.sub.6 alkyl.

[0139] The ligands of formula (II-A), (III) and (IV) are described in EP2607381A1 while the preparation of a reversible cross-linking agent of formula (I) comprising the ligand (II-B) is described in the present experimental part.

[0140] At least one group multidentate organic C ligand is present in the reversible cross-linking agent of formula (I) but two or more ligands C, equal or different from each other, may be present.

[0141] In a preferred embodiment, only one C ligand is present in the reversible cross-linking agent of formula (I).

[0142] In one embodiment, in the reversible cross-linking agent of formula (I)

A-B-C (I)

only one A group is present, only one C ligand and B group is absent.

[0143] In a preferred embodiment, in the reversible cross-linking agent of formula (I)

A-B-C (I)

only one A group is present, only one C ligand and B group is present and is divalent.

[0144] Particularly preferred reversible cross-linking agents are the agents of formula (I) wherein A=SH or norbornyl, B=O(CH.sub.2).sub.1-11 and C=a bis(benzimidazol)pyridyl, in particular 2,6-bis(1-methylbenzimidazol-2-yl)-pyridine-4-yl.

[0145] The elastomeric composition according to the invention preferably comprises at least 0.2 phr, at least 0.5 phr, more preferably at least 0.7 phr of at least one salt of a metal cation capable of forming complexes with the multidentate organic C ligand of the reversible cross-linking agent of formula (I).

[0146] Preferably, the elastomeric composition comprises not more than 10 phr, more preferably not more 7 phr of at least one salt of the metal cation, even more preferably not more 3 phr of at least one salt of the metal cation.

[0147] Preferably, the elastomeric composition comprises from 0.2 phr to 7 phr, more preferably from 0.7 phr to 3 phr of at least one salt of the metal cation.

[0148] Preferably, the elastomeric composition comprises not more than 6% by weight, more preferably not more than 3% by weight, even more preferably no more than 2% by weight of at least one salt of the metal cation.

[0149] Preferably, the molar ratio of reversible cross-linking agent (I) to the salt of the metal cation is between 6:1 and 0.5:1, more preferably between 4:1 and 1:1, even more preferably between 4:1 and 2:1.

[0150] Such ratio varies according to the type of multidentate C ligand and the metal cation. Preferably, the molar ratio between the reversible cross-linking agent of formula (I) and the salt of the metal cation is the stoichiometric one which allows the formation of the most effective complex in giving the desired reversible cross-linking, i.e. the one in which the metal cation is complexed by at least two C ligand groups belonging to different molecules of reversible cross-linking agents of formula (I), in turn bound to the elastomeric polymer.

[0151] The aforesaid stoichiometric ratio between the reversible cross-linking agent of formula (I) and the salt of the metal cation depends on the coordination number of the metal cation and on the coordination centres of the ligand, and is typically between 2:1 and 4:1. However, it is possible that in the compound the ligand or the metal are not completely involved in forming the desired complexes, therefore it will be possible and technologically convenient to select ratios other than the theoretical stoichiometric ones.

[0152] The elastomeric composition according to the invention may comprise a salt of the metal cation or more in mixture.

[0153] The salt of the metal cation comprises a metal cation and an anion.

[0154] The metal cation may be any metal cation capable of forming complexes with ligands.

[0155] The metal cation is preferably a divalent or trivalent cation, more preferably divalent. Preferably, the metal cation is selected from alkaline earth metals (2A group), transition metals and lanthanides, more preferably from Cu.sup.2+, Fe.sup.2+, Zn.sup.2+, Mg.sup.2+, Ca.sup.2+, Ru.sup.3+, Tb.sup.3+ and Eu.sup.3+, even more preferably it is selected from Zn.sup.2+ or Tb.sup.3+.

[0156] The elastomeric composition according to the invention may furthermore comprise possible other salts which are not however capable of forming complexes with the multidentate organic C ligand of the reversible cross-linking agent of formula (I), such as for example zinc stearate and zinc octoate.

[0157] The anion of the salt of the metal cation according to the invention is preferably a non-coordinating or weakly coordinating anion (WCA).

[0158] By the term weakly coordinating anion, now commonly used in general chemistry, it is meant to indicate those anions that interact weakly with cations, typically having the charge delocalised on the whole surface of the anion rather than localised on a specific atom. The properties characterising a weakly coordinating anion are reported for example in Chem. Rev. (1993), 93 (3), 927-942, in particular on page 929, par. II, subpar. C.

[0159] Preferably, the anion of the salt of the metal cation is an anion which tends to complex the metal cation more weakly than the C ligand of the present reversible cross-linking agent of formula (I). In the present experimental part (Example 2, Table 1) a possible method is illustrated, useful to guide the skilled in the art in the selection of suitable anions, based on complexation studies.

[0160] Some examples of weakly coordinating anions are described in Chem. Rev. (1993), 93 (3), 927-942; Angew. Chem. Int. Edit. (2004), 43 (16), 2066-2090; Angew. Chem. Int. Edit. (2018), 57 (43), 13982-14024; Chem. Soc. Rev. (2016), 45, 789-899.

[0161] Examples of suitable anions are tosylate, triflate, bistriflimide and borates, including perfluorinated ones.

[0162] Preferably, the anion is triflate.

[0163] Preferably, the salt of the metal cation comprises the metal cation Zn.sup.2+ or Th.sup.3+ and a weakly coordinating anion selected from tosylate, bistriflimide, triflate, more preferably the salt of the metal cation is zinc triflate.

[0164] Preferably, the salt of the metal cation is rather soluble in the elastomeric polymer of the present composition.

[0165] The elastomeric composition for tyres according to the present invention may comprise at least 0.5 phr of at least one reinforcing filler.

[0166] The present composition may comprise from 1 phr to 150 phr, from 5 phr to 120 phr or from 10 phr to 90 phr of at least one reinforcing filler.

[0167] Preferably, the reinforcing filler is selected from carbon black, white fillers, silicate fibres, derivatives thereof and mixtures thereof.

[0168] In an embodiment, said reinforcingfiller is a white filler selected from among hydroxides, oxides and hydrated oxides, salts and hydrated salts of metals, silicates fibres, derivatives thereof and mixtures thereof. Preferably, said white filler is silica. Preferably, said silica may be present in the elastomeric composition in an amount ranging between 1 phr and 100 phr, more preferably between 30 phr and 70 phr.

[0169] Commercial examples of suitable silica are Zeosil 1165 MP, Zeosil 1115 MP, Zeosil 185 GR, Efficium from Solvay, Newsil HD90 and Newsil HD200 from Wuxi, K160 and K195 from Wilmar, H160AT and H180 AT from IQE, Zeopol 8755 and 8745 from Huber, Perkasil TF100 from Grace, Hi-Sil EZ 120 G, EZ 160G, EZ 200G from PPG, Ultrasil 7000 GR and Ultrasil 9100 GR from Evonik.

[0170] In one embodiment, said reinforcing filler comprises silica mixed with carbon black.

[0171] In one embodiment, said reinforcing filler comprises a modified silica.

[0172] Silica can be modified for example by reaction with silsequioxanes (as in WO2018078480A1), by reaction with pyrroles (as in WO2016050887A1) or by reaction with silanising agents, such as bis(triethoxysilylpropyl)tetrasulphide (TESPT), 3-aminopropyltriethoxysilane (APTES) 3-glycidyloxypropyltriethoxysilane triethoxy(octyl)silane, triethoxy(ethyl)silane, triethoxy-3-(2-imidazolin-1-yl)propylsilane, triethoxy-p-tolylsilane, triethoxy(1-phenylethenyl)silane, triethoxy-2-thienylsilane, 1H,1H,2H,2H-perfluorooctyltriethoxysilane, 3-(triethoxysilyl)propyl isocyanate, 1H,1H,2H,2H-perfluorodecylthriethoxysilane, isobutyltriethoxysilane, n-octadecyltriethoxysilane, (3-chloropropyl)triethoxysilane, triethoxysilane and 3-(triethoxysilyl)propionitrile.

[0173] Commercial examples of suitable silanising agents are Si69, Dynasilan AMEO and Dynasilan GLYEO from Evonik.

[0174] The modified silica may be a sulphurised silanised silica.

[0175] Sulphurised silanised silica is a silica prepared by reaction of a silica, such as fumed silica, precipitated amorphous silica, wet silica (hydrated silicic acid), anhydrous silica (anhydrous silicic acid), or mixtures thereof, or of a metal silicate, such as aluminium silicate, sodium silicate, potassium silicate, lithium silicate or mixtures thereof, with at least one sulphurised silanising agent.

[0176] The term sulphurised silanising agent indicates an organic derivative of silicon containing mercapto, sulphide, disulphide or polysulphide groups, said derivative being capable of reacting with the OH groups of silica.

[0177] A commercial example of suitable sulphurised silanised silica is Agilon 400 silica from PPG.

[0178] In one embodiment, said reinforcing filler comprises a modified silica mixed with carbon black.

[0179] In one embodiment, said reinforcing filler comprises silicates.

[0180] In one embodiment, said silicates are lamellar silicates, such as bentonites, alloysite, laponite, saponite, vermiculite or hydrotalcite.

[0181] In one embodiment, said silicates are modified lamellar silicates analogously to what is described below for modified silicate fibres.

[0182] In one embodiment, said silicates are silicate fibres. These fibres typically have nano dimensions and have needle-like morphology.

[0183] The silicate fibres are preferably selected from sepiolite fibres, paligorskite fibres (also known as attapulgite), wollastonite fibres, imogolite fibres and mixtures thereof.

[0184] In one embodiment, said reinforcing filler comprises silicate fibres mixed with carbon black.

[0185] In one embodiment, said silicate fibres are modified silicate fibres.

[0186] In one embodiment, the modified silicate fibres can be for example fibres modified by acid treatment with partial removal of magnesium, such as those described and exemplified in patent application WO2016174629A1.

[0187] In one embodiment, the modified silicate fibres can be for example fibres modified by deposition of amorphous silica on the surface, such as those described and exemplified in patent application WO2016174628A1.

[0188] In one embodiment, the modified silicate fibres can be fibres organically modified by reaction, for example, with quaternary ammonium salts such as sepiolite fibres modified by reaction with talloyl benzyl dimethyl ammonium chloride marketed by Tolsa under the name Pangel B5.

[0189] In one embodiment, the modified silicate fibres can be fibres modified by reaction with a silanising agent selected for example from mono or bifunctional silanes with one or two or three hydrolysable groups such as bis-(3-triethoxysilyl-propyl)disulphide (TESPD), bis(3-triethoxysilyl-propyl)tetrasulphide (TESPT), 3-thio-octanoyl-1-propyl-triethoxysilane (NXT), Me.sub.2Si(OEt).sub.2, Me.sub.2PhSiCl, Ph.sub.2SiCl.sub.2.

[0190] In one embodiment, said reinforcing filler is carbon black.

[0191] Preferably, said carbon black is present in the elastomeric composition in an amount ranging between 1 phr and 100 phr, preferably between 5 phr and 70 phr. Preferably, the carbon black is selected from those having a surface area not smaller than 20 m.sup.2/g, preferably larger than 50 m.sup.2/g (as determined by STSAstatistical thickness surface area according to ISO 18852:2005).

[0192] Carbon black may be for example N110, N115, N121, N134, N220, N234, N326, N330, N375 or N550, N660 marketed by Birla Group (India) or by Cabot Corporation, Vulcan@ 1391 supplied by Cabot Corporation or Birla Carbon 2115 supplied by Birla Group.

[0193] The elastomeric composition for tyre compounds according to the invention may comprise from 0.1 to 10 phr of a vulcanising agent.

[0194] Preferably, the composition comprises at least 0.2 phr, 0.5 phr, 0.8 phr or 1 phr of at least one vulcanising agent.

[0195] Preferably, the composition comprises from 0.1 to 10 phr, from 0.2 to 10 phr, from 1 to 10 phr or from 1.5 to 5 phr of at least one vulcanising agent.

[0196] The at least one vulcanising agent is preferably selected from sulphur, sulphurised agents (sulphur donors), such as, for example, bis[(trialkoxysilyl)propyl]polysulphides, caprolactam-disulphide or peroxides and mixtures thereof.

[0197] Preferably, the vulcanising agent is sulphur, preferably selected from soluble sulphur (crystalline sulphur), insoluble sulphur (polymeric sulphur), (iii) oil-dispersed sulphur and mixtures thereof.

[0198] Commercial example of a vulcanising agent suitable for use in the elastomeric composition of the invention is the Redball Superfine sulphur of International sulphur Inc.

[0199] In the present elastomeric composition, the vulcanising agent may be used together with adjuvants such as vulcanisation activators, accelerants and/or retardants known to those skilled in the art.

[0200] The elastomeric composition according to the invention may optionally comprise at least one vulcanisation activator.

[0201] The vulcanisation activating agents suitable for use in the present elastomeric composition are zinc compounds, in particular ZnO, ZnCO.sub.3, zinc salts of saturated or unsaturated fatty acids containing from 8 to 18 carbon atoms, which are preferably formed in situ in the elastomeric composition by reaction of ZnO and of the fatty acid or mixtures thereof. For example, zinc stearate is used, preferably formed in situ in the elastomeric composition, by ZnO and fatty acid, or magnesium stearate, formed by MgO, or mixtures thereof.

[0202] The vulcanisation activating agents may be present in the elastomeric composition of the invention in amounts preferably from 0.2 phr to 15 phr, more preferably from 1 phr to 5 phr.

[0203] Preferred activating agents derive from the reaction of zinc oxide and stearic acid.

[0204] An example of activator is the product Aktiplast ST marketed by Rheinchemie.

[0205] The elastomeric composition according to the invention may further comprise at least one vulcanisation accelerant.

[0206] Vulcanisation accelerants that are commonly used may be for example selected from dithiocarbamates, guanidines, thioureas, thiazoles, sulphenamides, sulphenimides, thiurams, amines, xanthates, or mixtures thereof.

[0207] Preferably, the accelerant agent is selected from mercaptobenzothiazole (MBT), N-cyclohexyl-2-benzothiazol-sulphenamide (CBS), N-tert-butyl-2-benzothiazol-sulphenamide (TBBS) and mixtures thereof.

[0208] Commercial examples of accelerants suitable for use in the present elastomeric composition are N-cyclohexyl-2-benzothiazyl-sulphenamide Vulkacit (CBS or CZ), and N-terbutyl 2-benzothiazil sulphenamide, Vulkacit NZ/EGC marketed by Lanxess.

[0209] Vulcanisation accelerants may be used in the present elastomeric composition in an amount preferably from 0.05 phr to 10 phr, preferably from 0.1 phr to 7 phr, more preferably from 0.5 phr to 5 phr.

[0210] The elastomeric composition according to the invention may optionally comprise at least one vulcanisation retardant agent.

[0211] The vulcanisation retardant agent suitable for use in the present elastomeric composition is preferably selected from urea, phthalic anhydride, N-nitrosodiphenylamine N-cyclohexylthiophthalimide (CTP or PVI) and mixtures thereof.

[0212] A commercial example of a suitable retardant agent is N-cyclohexylthiophthalimide VULKALENT G of Lanxess.

[0213] The vulcanisation retardant agent may be present in the present elastomeric composition in an amount of preferably from 0.05 phr to 2 phr.

[0214] The present elastomeric composition may comprise one or more vulcanisation retardant agents as defined above in a mixture.

[0215] The elastomeric composition according to the invention may further comprise at least 0.05 phr, preferably at least 0.1 phr or 0.5 phr, more preferably at least 1 phr or 2 phr of at least one silane coupling agent.

[0216] Preferably, the elastomeric composition according to the invention comprises from 0.1 phr to 20.0 phr or from 0.5 phr to 10.0 phr, even more preferably from 1.0 phr to 5.0 phr of at least one silane coupling agent.

[0217] Preferably, said coupling agent is a silane coupling agent selected from those having at least one hydrolysable silane group which may be identified, for example, by the following general formula (III):

(R).sub.3SiC.sub.nH.sub.2nX (III)

wherein the groups R, equal or different from each other, are selected from: alkyl, alkoxy or aryloxy groups or from halogen atoms, provided that at least one of the groups Ris an alkoxy or an aryloxy group; n is an integer of from 1 to 6; X is a group selected from: nitrose, mercapto, amino, epoxide, vinyl, imide, chloro, (S).sub.mC.sub.nH.sub.2nSi(R).sub.3 and SCOR, wherein m and n are integers of from 1 to 6 and the R groups are as defined above.

[0218] Particularly preferred silane coupling agents are bis(3-triethoxysilylpropyl)tetrasulphide and bis(3-triethoxysilylpropyl)disulphide. Said coupling agents may be added as such or in mixture with an inert filler (such as carbon black) so as to facilitate their incorporation into the elastomeric composition.

[0219] An example of the silane coupling agent is TESPT: bis(3-triethoxysilylpropyl)tetrasulphide Si69 marketed by Evonik.

[0220] The elastomeric composition according to the invention may further comprise one or more additional ingredients, commonly used in the field, such as for example plasticising oils, resins, antioxidant and/or antiozonating agents (anti-aging agents), waxes, adhesives and the like.

[0221] For example, the elastomeric composition according to the present invention, in order to further improve the workability of the compound, may further comprise at least one plasticising oil.

[0222] The amount of plasticiser is preferably in the range from 5 to 25 phr, preferably from 8 to 20 phr.

[0223] The term plasticising oil means a process oil derived from petroleum or a mineral oil or a vegetable oil or a synthetic oil or combinations thereof.

[0224] The plasticising oil may be a process oil derived from petroleum selected from paraffins (saturated hydrocarbons), naphthenes, aromatic polycyclic and mixtures thereof.

[0225] Examples of suitable process oils derived from petroleum are aromatic, paraffinic, naphthenic oils such as MES (Mild Extract Solvated), DAE (Distillate Aromatic Extract), TDAE (Treated Distillate Aromatic Extract), TRAE (Treated Residual Aromatic Extract), RAE (Residual Aromatic Extract) known in the industry.

[0226] The plasticising oil may be an oil of natural or synthetic origin derived from the esterification of glycerol with fatty acids, comprising glycerine triglycerides, diglycerides, monoglycerides or mixtures thereof.

[0227] Examples of suitable vegetable oils are sunflower, soybean, linseed, rapeseed, castor and cotton oil.

[0228] The plasticising oil may be a synthetic oil selected from among the alkyl or aryl esters of phthalic acid or phosphoric acid.

[0229] The elastomeric composition according to the present invention may further comprise at least one resin.

[0230] The resin is a non-reactive resin, preferably selected from among hydrocarbon resins, phenolic resins, natural resins and mixtures thereof.

[0231] The amount of resin is preferably in the range from 5 to 25 phr, more preferably from 7 to 20 phr.

[0232] The elastomeric composition according to the invention may optionally comprise at least one wax.

[0233] The wax may be for example a petroleum wax or a mixture of paraffins.

[0234] Commercial examples of suitable waxes are the Repsol N-paraffin mixture and the Antilux 654 microcrystalline wax from Rhein Chemie.

[0235] The wax may be present in the elastomeric composition of the invention in an overall amount generally from 0.1 phr to 20 phr, preferably from 0.5 phr to 10 phr, more preferably from 1 phr to 5 phr.

[0236] The elastomeric composition according to the invention may optionally comprise at least one antioxidant agent.

[0237] The antioxidant agent is preferably selected from N-isopropyl-N-phenyl-p-phenylenediamine (IPPD), N-(-1,3-dimethyl-butyl)-n-phenyl-p-phenylenediamine (6PPD), N,N-bis-(1,4-dimethyl-pentyl)-p-phenylenediamine (77PD), N,N-bis-(1-ethyl-3-methyl-pentyl)-p-phenylenediamine (DOPD), N,N-bis-(1,4-dimethyl-pentyl)-p-phenylenediamine, N,N-diphenyl-p-phenylenediamine (DPPD), N,N-ditolyl-p-phenylenediamine (DTPD), N,N-di-beta-naphthyl-p-phenylenediamine (DNPD), N,N-bis(1-methylheptyl)-p-phenylenediamine, N,N-Di-sec-butyl-p-phenylenediamine (44PD), N-phenyl-N-cyclohexyl-p-phenylenediamine, N-phenyl-N-1-methylheptyl-p-phenylenediamine and the like, and mixtures thereof, preferably it is N-1,3-dimethylbutyl-N-phenyl-p-phenylenediamine (6-PPD).

[0238] A commercial example of a suitable antioxidant agent is 6PPD from Solutia or Santoflex produced by Eastman.

[0239] The antioxidant agent may be present in the elastomeric composition in an overall amount preferably from 0.1 phr to 20 phr, more preferably from 0.5 phr to 10 phr.

[0240] A further aspect of the present invention is a vulcanised elastomeric compound for tyres obtained by mixing and vulcanising the elastomeric composition according to the invention.

[0241] The elastomeric compound of the invention is characterised by a particular hysteresis pattern.

[0242] In fact, unlike conventional elastomeric compounds (for example reference compound 1, FIG. 4a) where the hysteresis has a decreasing monotonic pattern as T increases, the compound of the invention instead has non-decreasing Tan delta values (for example compound 3, FIG. 4c) or even increasing (for example compound 2, FIG. 4b) as the T increases, i.e. once the temperature corresponding to normal driving has been exceeded and thus one has entered into the sports driving speed. The comparison between the Tan delta pattern of compounds 1-3 is shown in the summary FIG. 5.

[0243] Furthermore, the elastomeric compound of the invention (2, 3) has improved static properties at break (see Table 3), maintaining modules and hardnesses close to those of the reference compound, thus showing that the reversible cross-linking agent of the invention does not distort the properties of the compound in which it is inserted, in particular it does not induce cold hardening of the compound, as instead occurs with the functionalised SBRs described in Macromolecules (2016), 49, 1781-1789.

[0244] A further aspect of the present invention is a process for preparing the vulcanised elastomeric compound according to the invention, comprising a first non-productive step and a second productive step, preferably comprising: [0245] in the first non-productive step, mixing at least one diene elastomeric polymer, at least one reinforcing filler and at least one reversible cross-linking agent of formula (I) and possibly at least one antioxidant, a vulcanisation activating agent, a compatibilising agent, an antiozonant and/or a wax, preferably at a temperature between 110 and 190 C., to give a first elastomeric compound, [0246] in the second productive step, adding to the first elastomeric compound at least one vulcanising agent, at least one salt of the metal cation and possibly at least one accelerant agent, a retardant agent, a compatibilising agent, a vulcanisation activating agent and/or a peroxide, and mixing the components at a temperature preferably lower than 120 C., to give a vulcanisable elastomeric compound, and [0247] vulcanising the vulcanisable elastomeric compound, at a temperature preferably between 150 C. and 200 C., to give the vulcanised elastomeric compound.

[0248] In one embodiment of the present process, the reversible cross-linking agent of formula (I) and the salt of the metal cation are both added in the first non-productive step.

[0249] In an embodiment of the present process, the reversible cross-linking agent of formula (I) and the salt of the metal cation are both added in the second productive step.

[0250] In a preferred embodiment of the present process, the reversible cross-linking agent of formula (I) is added in the first non-productive step while the metal cation salt in the second productive step.

[0251] In an embodiment of the present process, the reversible cross-linking agent of formula (I) and the salt of the metal cation are made to pre-react, i.e. the complex between the reversible cross-linking agent of formula (I) and the metal cation is prepared first and, subsequently, the preformed complex is added and mixed in the second productive step.

[0252] The process according to the invention typically comprises one or more thermomechanical mixing steps in at least one suitable mixer, in particular at least a first mixing step (step 1non-productive) and a second mixing step (step 2productive) as defined above.

[0253] Each mixing step may comprise several intermediate processing steps or sub-steps, characterised by the momentary interruption of the mixing to allow the addition of one or more ingredients but without intermediate discharge of the compound.

[0254] The mixing may be performed, for example, using an open mixer of the open-mill type or an internal mixer of the type with tangential rotors (Banbury) or with interpenetrating rotors (Intermix), or in continuous mixers of the Ko-Kneader type (Buss) or of the twin-screw or multi-screw type.

[0255] Generally, but not necessarily, at the end of step 1 the first elastomeric compound is discharged and after a variable period of time it is recharged in the same or another suitable mixer, for the subsequent productive step 2.

[0256] In productive step 2, the temperature is generally controlled to avoid undesired pre-vulcanisation phenomena.

[0257] At the end of the second step, the vulcanisable elastomeric compound is incorporated into one or more components of the green tyre, preferably in the tread band, and subjected to vulcanisation, according to known techniques.

[0258] Any of the usual vulcanisation processes may be used in the present process, such as heating in a press or mould, heating with superheated steam or hot air.

[0259] The tyres may be built, formed, moulded and vulcanised with various methods known to the skilled in the art.

[0260] A further aspect of the present invention is a tyre component for vehicle wheels comprising, or preferably consisting of, an elastomeric compound according to the invention, preferably selected from the tread band, under-layer, anti-abrasive strip, sidewall, sidewall insert, mini-sidewall, liner, under-liner, rubber layers, bead filler, bead reinforcing layers (flipper), bead protection layers (chafer), sheet. Preferably, the tyre component is a tread band, an anti-abrasive strip or a sidewall.

[0261] The green tyre component is produced with the vulcanisable elastomeric compound and then vulcanised, preferably together with the other components, to give the vulcanised tyre component.

[0262] A further aspect of the present invention is a tyre for vehicle wheels comprising at least one of the components according to the invention.

[0263] Preferably, said component is a tread band.

[0264] In one embodiment, a tyre for vehicles according to the present invention comprises at least [0265] a carcass structure comprising at least a carcass ply having opposite lateral edges associated to respective bead structure; [0266] possibly a pair of sidewalls applied to the lateral surfaces of the carcass structure, respectively, in an axially outer position; [0267] possibly a belt structure applied in radially outer position with respect to the carcass structure; [0268] a tread band applied in a radially outer position to said carcass structure or, if present, a belt structure, [0269] possibly a layer of elastomeric material, referred to as under-layer, applied in a radially inner position with respect to said tread band,
wherein at least one component, preferably the tread band, the anti-abrasive strip and/or the sidewalls, comprise, or preferably consist of, the elastomeric compound according to the invention.

[0270] The tyre according to the invention may be for summer, winter use or for all seasons.

[0271] In one embodiment, the tyre according to the invention is a tyre for a passenger car, with normal or high performance or for off-road vehicles, preferably a tyre for passengers, conceived for vehicles for personal use, such as sedans, coupes, crossovers, SUVs, minivans and small pickups.

[0272] In one embodiment, the tyre according to the invention is a tyre for motorcycles, wherein at least one component comprises, or preferably consists of, the elastomeric compound according to the invention.

[0273] The tyre according to the invention may be a tyre for two, three or four-wheeled vehicles.

[0274] In one embodiment, the tyre according to the invention is a tyre for bicycle wheels.

[0275] A tyre for bicycle wheels typically comprises a carcass structure turned around a pair of bead cores at the beads and a tread band arranged in a radially outer position with respect to the carcass structure. Preferably, at least the tread band comprises the elastomeric compound according to the invention.

[0276] The tyre according to the present invention may be produced according to a process which comprises: [0277] building components of a green tyre on at least one forming drum; [0278] shaping, moulding and vulcanising the tyre;
wherein building at least one of the components of a green tyre comprises: [0279] manufacturing at least one green component, preferably the tread band, comprising, or preferably consisting of, the vulcanisable elastomeric compound of the invention.

Description of a Tyre According to the Invention

[0280] A tyre for vehicle wheels according to the invention, comprising at least one component comprising the present elastomeric compound, is illustrated in radial half-section in FIG. 1.

[0281] In FIG. 1, a indicates an axial direction and X indicates a radial direction, in particular X-X indicates the outline of the equatorial plane. For simplicity, FIG. 1 shows only a portion of the tyre, the remaining portion not shown being identical and arranged symmetrically with respect to the equatorial plane X-X.

[0282] The tyre (100) for four-wheeled vehicles comprises at least one carcass structure, comprising at least one carcass layer (101) having respectively opposite end flaps engaged with respective annular anchoring structures (102), referred to as bead cores, possibly associated to a bead filler (104).

[0283] The tyre area comprising the bead core (102) and the filler (104) forms a bead structure (103) intended for anchoring the tyre onto a corresponding mounting rim, not shown.

[0284] The carcass structure is usually of radial type, i.e. the reinforcing elements of the at least one carcass layer (101) lie on planes comprising the rotational axis of the tyre and substantially perpendicular to the equatorial plane of the tyre. Said reinforcing elements generally consist of textile cords, such as rayon, nylon, polyester (for example polyethylene naphthalate, PEN). Each bead structure is associated to the carcass structure by folding back of the opposite lateral edges of the at least one carcass layer (101) around the annular anchoring structure (102) so as to form the so-called carcass flaps (101a) as shown in FIG. 1.

[0285] In one embodiment, the coupling between the carcass structure and the bead structure can be provided by a second carcass layer, not shown in FIG. 1, applied in an axially outer position with respect to the first carcass layer.

[0286] An anti-abrasive strip (105) possibly made with elastomeric material is arranged in an outer position of each bead structure (103).

[0287] The carcass structure is associated to a belt structure (106) comprising one or more belt layers (106a), (106b) placed in radial superposition with respect to one another and with respect to the carcass layer, having typically textile and/or metallic reinforcing cords incorporated within a layer of elastomeric material.

[0288] Such reinforcing cords may have crossed orientation with respect to a direction of circumferential development of the tyre (100). By circumferential direction it is meant a direction generally facing in the direction of rotation of the tyre.

[0289] At least one zero-degree reinforcing layer (106c), commonly known as a 0 belt, may be applied in a radially outermost position to the belt layers (106a), (106b), which generally incorporates a plurality of elongated reinforcing elements, typically metallic or textile cords, oriented in a substantially circumferential direction, thus forming an angle of a few degrees (such as an angle of between about 0 and 6) with respect to a direction parallel to the equatorial plane of the tyre, and coated with an elastomeric material.

[0290] A tread band (109) comprising the elastomeric compound according to the invention is applied in a position radially outer to the belt structure (106).

[0291] Moreover, respective sidewalls (108) of elastomeric material are applied in an axially outer position on the lateral surfaces of the carcass structure, each extending from one of the lateral edges of tread (109) at the respective bead structure (103).

[0292] In a radially outer position, the tread band (109) has a rolling surface (109a) intended to come in contact with the ground. Circumferential grooves, which are connected by transverse notches (not shown in FIG. 1) so as to define a plurality of blocks of various shapes and sizes distributed over the rolling surface (109a), are generally made on this surface (109a), which for simplicity is represented smooth in FIG. 1.

[0293] An under-layer (111) of elastomeric material may be arranged between the belt structure (106) and the tread band (109).

[0294] A strip consisting of elastomeric material (110), commonly known as mini-sidewall, can optionally be provided in the connecting zone between the sidewalls (108) and the tread band (109), this mini-sidewall being generally obtained by co-extrusion with the tread band (109) and allowing an improvement of the mechanical interaction between the tread band (109) and the sidewalls (108). Preferably, the end portion of the sidewall (108) directly covers the lateral edge of the tread band (109).

[0295] In the case of tubeless tyres, a rubber layer 112, generally known as liner, which provides the necessary impermeability to the inflation air of the tyre, can also be provided in a radially internal position with respect to the carcass layer 101.

[0296] The rigidity of the tyre sidewall 108 may be improved by providing the bead structure 103 with a reinforcing layer 120 generally known as flipper or additional strip-like insert.

[0297] The flipper 120 is a reinforcing layer which is wrapped around the respective bead core 102 and the bead filler 104 so as to at least partially surround them, said reinforcing layer being arranged between the at least one carcass layer 101 and the bead structure 103. Usually, the flipper is in contact with said at least one carcass layer (101) and said bead structure (103).

[0298] The flipper 120 typically comprises a plurality of textile cords incorporated within a layer of elastomeric material.

[0299] The reinforcing annular structure or bead (103) of the tyre may comprise a further protective layer which is generally known by the term of chafer (121) or protective strip and which has the function of increasing the rigidity and integrity of the bead structure (103).

[0300] The chafer (121) usually comprises a plurality of cords incorporated within a rubber layer of elastomeric material. Such cords are generally made of textile materials (such as aramide or rayon) or metal materials (such as steel cords).

[0301] A layer or sheet of elastomeric material can be arranged between the belt structure and the carcass structure (not shown). The layer may have a uniform thickness. Alternatively, the layer may have a variable thickness in the axial direction. For example, the layer may have a greater thickness close to its axially outer edges with respect to the central (crown) zone.

[0302] Advantageously, the layer or sheet may extend on a surface substantially corresponding to the extension surface of said belt structure.

[0303] In a preferred embodiment, a layer of elastomeric material, referred to as under-layer (111), may be placed between said belt structure and said tread band, said under-layer preferably extending on a surface substantially corresponding to the extension surface of said belt structure.

[0304] The elastomeric compound according to the present invention may advantageously be incorporated in one or more of the above tyre components, preferably in the tread band, in the anti-abrasive strip or in the sidewall.

[0305] The building of the tyre (100) as described above, may be carried out by assembling respective semi-finished products consisting of the respective green compounds, semi-finished products adapted to form the components of the tyre, on a forming drum, not shown, by at least one assembling device.

[0306] At least a part of the components intended to form the carcass structure of the tyre may be built and/or assembled on the forming drum. More particularly, the forming drum is intended to first receive the possible liner, and then the carcass structure. Thereafter, devices non shown coaxially engage one of the annular anchoring structures around each of the end flaps, position an outer sleeve comprising the belt structure and the tread band in a coaxially centred position around the cylindrical carcass sleeve and shape the carcass sleeve according to a toroidal configuration through a radial expansion of the carcass structure, so as to cause the application thereof against a radially inner surface of the outer sleeve.

[0307] After building of green tyre, a moulding and vulcanisation treatment is generally carried out in order to determine the structural stabilisation of the tyre through cross- linking of the elastomeric compositions, as well as to impart a desired tread pattern on the tread band and to impart any distinguishing graphic signs at sidewalls.

EXPERIMENTAL PART

Methods of Analysis

Thermogravimetric Analysis (TGA)

[0308] The thermogravimetric measurements were carried out with a Mettler-Toledo STAR device under inert conditions under an atmosphere of N.sub.2 and on samples weighing between 8 and 10 mg. The measurement contemplated a constant increase of 10 /min in the temperature range of from 25 to 600 C.

Differential Scanning Calorimetric Analysis (DSC)

[0309] The calorimetry measurements were carried out with a Mettler-Toledo STAR device under inert conditions under an atmosphere of N.sub.2 and on samples weighing between 8 and 10 mg. The measurement included heating/cooling cycles at a rate of 10 C./min in the temperature range from 80 to +250 C.

Spectrophotometric Analysis (UV-VIS)

[0310] The spectrophotometric measurements were carried out with a Shimadzu UV-2401 PC spectrophotometer, in Acetonitrile or in Chloroform: Acetonitrile (9:1). For the measurements, quartz cuvettes (1 cm) produced by Hellma were used.

.SUP.1.H-NMR Assay

[0311] Nuclear magnetic resonance (NMR) spectroscopy was conducted with a Bruker Avance DPX 400 spectrometer at frequencies of 400.19 MHz for .sup.1H and 100.63 MHz for .sup.13C. The spectra obtained were calibrated on the residual signal of the solvent used (CD.sub.2Cl.sub.2: 5.32 ppm .sup.1H; 53.84 ppm .sup.13C). The data were processed using the MestReNova software (v 11.0) and all chemical shifts are reported in parts per million (ppm) with coupling constants in Hz (multiplicity: s=singlet, d=doublet, dd=doublet of doublets, t=triplet, dt=doublet of triplets, ddd=doublet of doublets of doublets, sep=septuplet, m=multiplet, br=broad signal).

Mass Analysis

[0312] High resolution mass spectrometry was conducted with an ESI-MS Bruker FTMS 4.7 T BioAPEX II instrument equipped with ComiSource 1.0 and operating in positive ionization mode.

Measurement of Static Mechanical Properties

[0313] The static mechanical properties were measured with a Zwick/Roell Z010 instrument equipped with 200N and 5N capacity cells, on Dumbell specimens of dimensions 3850.10.3 mm (lengthwidththickness) prepared by vulcanisation (at 150 C.for 30 min) of the elastomeric compounds to be examined. In the measurement, a preload of 0.01 MPa was applied for 30 seconds and subsequently a constant deformation of 200%/min, where the percentage refers to the length of the sample under examination calculated from the distance between the two clamps.

Dynamic Mechanical Analysis (DMA)

[0314] The dynamic modulus was measured with a TA Instruments DMA Q800 equipment set in thin film voltage mode, suitable for measuring rectangular specimens of dimensions 5155.60.10.5 mm (lengthwidththickness).

[0315] In the low deformation DMA measurement, the method involved the application of a sinusoidal dynamic deformation of an amplitude equal to 0.25% with respect to the length under preload of 0.01 MPa, at a frequency of 1 Hz, and at the same time of a ramp of temperature with constant increase of 3 C./min from 80 C. to +170 C.

[0316] In the high deformation DMA measurement, to the sample placed under constant temperature of 70 C., and 25% pre-load, where the percentage refers to the length of the sample being examined calculated from the distance between the two clamps, a sinusoidal dynamic deformation with an amplitude equal to 3.5% with respect to the length under pre-load was applied, at a frequency of 10 Hz, until the equilibrium of the dynamic elastic modulus (E) was reached, typically identifiable after an application of 45 minutes, such as reaching a constant value (less than 0.05% variation in 5 minutes) of E. Once the dynamic equilibrium of the material was reached, a temperature ramp with a constant increase of 3 C./min from 80 C. to +170 C. was applied.

[0317] The dynamic elastic properties were expressed in terms of dynamic elastic modulus (E) and tan delta (loss factor).

Evaluation of Cross-Linking: Swelling Test

[0318] The swelling test was carried out by immersing the sample under examination with dimensions equal to 105.60.3 mm (lengthwidththickness) and weight between 22 and 27 mg, in a cyclohexane solution and evaluating the weight variation, at defined intervals (10, 15, 20, 25, 30, 35, 90 minutes), with respect to the dry sample. In order to evaluate the actual cross-linking given by the coordination complexes, after the initial weighing at defined intervals of the sample soaked in cyclohexane alone, a MeBIP ligand antagonist (in this case the TMEDA ligand) was added to the same solution. The sample under examination was then weighed again at defined intervals of 45, 60, 150 minutes.

Example 1: Preparation and Characterisation of Cross-Linking Agents of Formula (I)

Example 1a: Norb-MeBIP Preparation

[0319] The reversible cross-linking agent of formula

##STR00006##

wherein A=norbornene, B=OCH.sub.2, C=MeBIP and wherein MeBIP indicates the 2,6-bis(1-methylbenzimidazol-2-yl)-pyridine-4-yl (II-B) group

##STR00007##

was prepared according to the following synthesis scheme 2:

##STR00008##

[0320] Intermediate (1) was prepared as described below.

[0321] 5-Norbornene-2-methylthosylate was prepared by reaction between 5-Norbornene-methanol (1 eq), p-Toluensulfonyl chloride (1.2 eq) and triethylamine (1.5 eq) in dichloromethane (1.5 M) at room temperature for 16 hours. When the reaction was complete, the solution was diluted with dichloromethane and extracted with water, then the organic phase was concentrated under vacuum. The residue was purified by means of a chromatographic column using a 9:1 pentane:ethyl-acetate solution as eluent, obtaining the pure product with quantitative yield.

[0322] Intermediate (1) (1 eq) was converted to the reversible cross-linking agent (IB) Norb-MeBIP by reaction with 5-Norbornene-2-methyltosylate (1.2 eq) and potassium carbonate (3 eq) under reflux in Acetonitrile (0.3 M) for 16 h. When the reaction was complete, the solution was extracted with water and dichloromethane, then the organic phase was dried under vacuum. The pure product was obtained by vapour diffusion crystallization, placing the container with the concentrated organic solution of the raw product inside a larger container into which diethyl ether was then added. The larger container was then sealed in order to keep the vapours of the two solvents inside the chamber, with a yield of 92%.

Example 1b: Ligand (I-C) HS-MeBIP Preparation

[0323] The reversible cross-linking agent of formula

##STR00009##

wherein A=HS, B=O(CH.sub.2).sub.11, C=MeBIP, [0324] was prepared according to the following synthesis scheme 3:

##STR00010## ##STR00011## ##STR00012##

[0325] Intermediate 1 (HO-MeBIP) was prepared following the procedure described by Rowan and Beck [Metal-legant induced supramolecular polymerization: A route to responsive materials. Faraday Discussions 128, 43-53, (2005)] (Step a: H.sub.3PO.sub.4, 200 C., yield 71%).

[0326] Intermediate 1 (1 eq) was then alkylated on the OH group with 1,11-dibromoundecane (1.2 eq) and potassium carbonate (3 eq) under reflux in Acetonitrile (0.3 M) for 16 h. When the reaction was complete, the solution was extracted with water and dichloromethane, then the organic phase was concentrated under vacuum. The pure product was obtained by vapour diffusion crystallization, placing the container with the concentrated organic solution of the raw product inside a larger container into which diethyl ether was then added. The larger container was then sealed in order to keep the vapours of the two solvents inside the chamber, obtaining intermediate 2 with a yield of 87%.

[0327] Finally, the derivative thiol (I-C, HS-MeBIP) was prepared directly by reaction of intermediate 2 (1 eq) with hexamethyldisilazane (1.2 eq) and 1M tetrabutylammonium fluoride in THF (1.1 eq at room temperature in anhydrous Tetrahydrofuran (0.5M) for 2 hours. When the reaction was complete, the solution was diluted with dichloromethane and extracted with water, then the organic phase was concentrated under vacuum. The pure product was obtained by vapour diffusion crystallization, placing the container with the concentrated organic solution of the raw product inside a larger container into which diethyl ether was then added. The larger container was then sealed in order to keep the vapours of the two solvents inside the chamber, with a quantitative yield.

[0328] The chemical structure of the reversible cross-linking agent (I-C) HS-MeBIP was confirmed by NMR spectroscopy and mass spectrometry:

[0329] 1H-NMR (400 MHZ, CD.sub.2Cl.sub.2, RT): =1.32 (m, 14H) 1.60 (m, 2H) 1.89 (m, 2H) 2.51 (dd, 2H) 4.26 (s, 6H) 4.27 (m, 2H) 7.34 (m, 2H) 7.39 (m, 2H) 7.50 (d, J=7.54 Hz, 2H) 7.81 (d, J=7.44 Hz, 2H) 7.98 (s, 2H); 13C NMR (400 MHZ, CD2CI2, RT): =167.23, 151.57, 150.77, 142.66, 137.81, 124.07, 123.31, 120.26, 112.45, 110.67, 69.52, 34.72, 33.18, 30.10, 30.08, 30.06, 29.87, 29.65, 29.49, 28.95, 26.45, 25.12; ESI-MS (pos.) M/z: calculated 542.3 exact 542.29106.

[0330] Thermal properties were evaluated by thermogravimetric analysis (TGA, FIG. 2a) and differential scanning calorimetric (DSC, FIG. 2b).

[0331] The reversible cross-linking agent HS-MeBIP (I-C) exhibited high thermal stability, with the onset of mass loss observed in TGA around 367 C. (FIG. 2a). The DSC traces showed a reversible melt transition around 150 C. and crystallisation at around 120 C. (FIG. 2b).

Example 2: Complexation Studies

[0332] The formation of complexes was studied by spectrophotometric titration with increasing metal/ligand (M/L) ratio. For greater operational simplicity in Examples 2a-2e the intermediate 2 was used as a ligand while in Example 2f, the corresponding reversible cross-linking agent of formula (I) was used.

[0333] Example 2a: adding aliquots (25 l) of a solution of Zn(OTf).sub.2 in ACN(c=125 mol/l) to a solution of intermediate 2 in ACN (c=22 mol/l) showed that the maximum absorption shifted from the wavelength of 314 nm, characteristic of the ligand (L), to 341 nm, the absorption band of the corresponding metal-ligand complex (ML) (FIG. 3a).

[0334] The graph of the absorption intensity at these wavelengths versus the metal/ligand ratio confirmed that the complex formation was complete after the addition of 0.5 equivalents of Zn.sup.2+ (FIG. 3b), corroborating the thesis of the formation of the desired complex with a metal/ligand ratio of 1:2 and showing that the triflate anion was a weaker coordinating anion than the ligand 2,6-Bis(1-methylbenzimidazol-2-yl)-pyridine-4-yl of Intermediate 2.

[0335] Example 2b: the addition of aliquots (50 l) of a solution of ZnCl.sub.2 in ACN (c=143.5 umol/l) to a solution of intermediate 2 in ACN (c=22 mol/l) showed, as for the example shown in FIG. 3a, that the maximum absorption shifted from the wavelength of 314 nm, characteristic of the ligand (L), to 341 nm, absorption band of the corresponding metal-ligand complex (ML) (FIG. 3c). The graph of the absorption intensity at these wavelengths versus the metal/ligand ratio showed that the complex formation was complete after the addition of 1 equivalent of Zn.sup.2+ (FIG. 3d), demonstrating that the use of a salt with a strongly coordinating anion penalised the formation of the desired 1:2 complex and instead led to the formation of a 1:1 complex, unsuitable for the purpose of the present invention.

[0336] Example 2c: the addition of aliquots (50 l) of a solution of Zn 2-ethylhexanoate in CHCl.sub.3/ACN (9:1) (c=144 mol/l) to a solution of intermediate 2 in CHCl.sub.3/ACN (9:1) (c=21.5 mol/l) showed, contrary to the previous examples shown in FIGS. 3a and 3c, that the characteristic absorption of the ligand (L), at 341 nm, did not show shifting after numerous additions of metal (FIG. 3e). The graph of the absorption intensity at these wavelengths versus the metal/ligand ratio showed that the complex formation was not completed although additions were made until 7 equivalents of Zn.sup.2+ were reached (FIG. 3f), demonstrating that the use of a salt with a strongly coordinating anion penalised the formation of the complex itself.

[0337] Example 2d: Repeating Example 2c with zinc stearate, the same strongly coordinating anion behaviour was observed (no complex formation of zinc with intermediate 2).

[0338] Example 2e: adding aliquots (25 l) of a solution of Tb(OTf).sub.3 in ACN (c=114,5 umol/l) to a solution of intermediate 2 in ACN (c=21.5 mol/l) showed that the maximum absorption shifted from the wavelength of 314 nm, characteristic of the ligand (L), to 341 nm, the absorption band of the corresponding metal-ligand complex (ML) (FIG. 3g). The graph of the absorption intensity at these wavelengths versus the metal/ligand ratio confirmed that the complex formation was complete after the addition of 0.33 equivalents of Tb.sup.3+ (FIG. 3h), corroborating the thesis of the formation of the desired complex, having a metal/ligand ratio of 1:3 typical in the case of using salts of trivalent metal ions with weakly coordinating anions.

[0339] Example 2f: the addition of aliquots (25 l) of a solution of Zn(NTf.sub.2).sub.2 (zinc bistriflimide) in CHCl.sub.3/ACN (9:1) (c=111.3 mol/l) to a solution of reversible cross-linking agent HS-MeBIP (I-C) in CHCl.sub.3/ACN (9:1) (c=25 mol/l) showed that the maximum absorption shifted from the wavelength of 314 nm, characteristic of the ligand (L), to 341 nm, the absorption band of the corresponding metal-ligand complex (ML) (FIG. 3i). The graph of the absorption intensity at these wavelengths versus the metal/ligand ratio confirmed that the complex formation was complete after the addition of 0.5 equivalents of Zn.sup.2+ (FIG. 31), corroborating the thesis of formation of complexes with a metal/ligand ratio of 1:2. The experiment showed that the presence of the (CF.sub.3SO.sub.2).sub.2N.sup. group, a weakly coordinating anion, did not interfere in any way with the complexation.

[0340] The conditions and results of the complexation tests of Examples 2a-2f are summarised in the following Table 1:

TABLE-US-00001 TABLE 1 Cross-linker/ Anion Metal Ligand Complex complexing Ex. (M) Salt anion (L) (ML) M/L force 2a Zn.sup.2+ triflate Int. 2 (MeBIP) Zn(MeBIP).sub.2 2:1 Weak 2b Zn.sup.2+ chloride Int. 2 (MeBIP) Zn(MeBIP)Cl 1:1 Strong 2c Zn.sup.2+ 2-ethyl Int. 2 (MeBIP) no no Very strong hexanoate 2d Zn.sup.2+ stearate Int. 2 (MeBIP) no no Very strong 2e Tb.sup.3+ triflate Int. 2 (MeBIP) Tb(MeBIP).sub.3 3:1 Weak 2f Zn.sup.2+ bistriflimidate HS-MeBIP Zn(MeBIP).sub.2 2:1 Weak
where triflate is the anion CF.sub.3SO.sub.3.sup. and bistriflimidate is the anion (CF.sub.3SO.sub.2).sub.2N.sup.. For the purposes of the invention, it is important that complexes may be formed in which at least two ligands coordinate to a metal centre.

Example 3: Preparation of the Zn Complex (HS-MeBIP).SUB.2

[0341] The complex between HS-MeBIP (I-C) and Zn.sup.2+, i.e. the Zn(HS-MeBIP).sub.2 complex represented herein

##STR00013##

where M.sup.2+ is Zn.sup.2+, was obtained on a preparative scale of 500 mg as a pale pink solid by adding 0.5 eq of Zn(OTf).sub.2 dissolved in methanol to a solution of the HS-MeBIP ligand dissolved in chloroform/methanol 9:1 at room temperature and subsequent evaporation of the solvent at 60 C. under vacuum (10.sup.4 mbar) for 16 hours.

[0342] The chemical structure of the complex was confirmed by NMR spectroscopy: 1H-NMR (400 MHZ, CD.sub.2Cl.sub.2, RT): =1.32 (m, 12H) 1.62 (m, 2H) 1.70 (m, 2H) 2.11 (m, 2H) 2.51 (dd, 2H) 4.34 (s, 6H) 4.65 (m, 2H) 6.54 (d, J=8.15 Hz, 2H) 7.12 (m, 2H) 7.31 (m, 2H) 7.44 (d, J=8.32 Hz, 2H) 8.10 (s, 2H).

Example 4

Preparation of Elastomeric Compounds

[0343] Reference elastomeric compounds and according to the invention were prepared, with the compositions reported in the following Table 2:

TABLE-US-00002 TABLE 2 elastomeric compositions (phr) Compositions 1 2 3 Step Ingredients Ref. Inv. Inv. 1 SBR 4602 100 100 100 6PPD 1 1 1 Stearic ac. 2 2 2 ZnO 2 2 2 Carbon black 40 40 40 Reversible cross- HS-MeBIP (I-C) Norb-MeBIP (I-B) linking agent 6.92 5.90 2 Sulphur 1 1 1 CBS 2.5 2.5 2.5 TiBTD 0.4 0.4 0.4 Triflate zinc 2.32 2.32 Key: Ref. = Standard reference compound; Inv. = Compound according to the invention; SBR 4602: styrene-butadiene elastomeric polymer (Mn: 300,000 Da) supplied by Trinseo; 6PPD: N-(1,3-dimethylbutyl)-N-phenyl-p-phenylenediamine supplied by Eastman Chemical Company; Stearic acid: supplied by SOGIS INDUSTRIA CHIMICA S.p.A, sulphur activator; ZnO: supplied by Empils-Zinc, sulphur activator; Carbon black: Vulcan 1391 supplied by Cabot Corporation, reinforcing filler; Cross-linking agents: HS-MeBIP (I-C) and Norb-MeBIP (I-B) prepared as described in Example 1b-1a; Sulphur: supplied by Zolfindustria vulcaniser; CBS: N-Cyclohexylbenzothiazol-2-sulphenamide, supplied by General Quimica SA accelerant; TiBTD: Diisobutyl-Thiuram-Disulphide, supplied by PUYANG WILLING CHEMICALS CO., LTD accelerant; Zinc triflate: supplied by Strem Chemicals, metal cation salt.

[0344] Starting from the elastomeric compositions 1-3 shown in Table 2, the corresponding elastomeric compounds were prepared according to the following process.

[0345] The mixing of the components was carried out in two steps using a Brabender Plastograph EC rheometer apparatus equipped with the Measuring Mixer 30 EHT mixing system with a total capacity of 30 ml.

[0346] In the first step (1), the SBR 4602, the 6PPD, the Stearic acid, ZnO, the reversible cross-linking agent and carbon black were introduced. Mixing at 60 rpm was continued for 5 minutes, at 130 C.

[0347] Subsequently, in the second step (2), carried out using the same mixer, sulphur, CBS, TiBTD and triflate zinc were added, and mixing at 60 rpm was continued for about 4 minutes at 70 C., when the vulcanisable compounds were discharged and vulcanised in a press at 150 C. for 30 min.

Characterisation of the Compounds

Static Mechanical Properties

[0348] The main static properties of the vulcanised elastomeric compounds 1-3, measured with the methods described above, are shown in the following Table 3:

TABLE-US-00003 TABLE 3 static properties of compounds 1-3 1 2 3 Compositions Ref. Inv. Inv. Reversible cross- HS-MeBIP Norb-MeBIP linking agent (1 mol %) (1 mol %) Salt Zn(OTf).sub.2 Zn(OTf).sub.2 E (MPa) 12.2 0.7 19.9 1.3 15.8 0.6 CR (MPa) 20.7 2.6 22.1 1.7 20.3 0.9 CA05 (MPa) 1.72 0.03 2.04 0.02 1.85 0.03 CA1 (MPa) 2.99 0.08 3.25 0.03 2.88 0.04 AR (%) 392 39 476 26 457 13 where E is Young's modulus, i.e. the modulus representing the resistance of the material to elastic deformation, calculated as the secant modulus in the deformation from 0 to 2%, CR is the load at break, CA05 and CA1 is the load for an elongation of 50% and 100% respectively, AR is the elongation at break.

[0349] As may be seen from the data reported in Table 3, the compounds 2 and 3 comprising the cross-linking system according to the invention show a Young's modulus E, a load at 50% elongation and above all an elongation at break higher than the reference compound, indicating on the one hand an increased level of overall cross-linking, keeping the other features comparable and on the other of an improvement in the balance between modulus and fragility: the extra cross-linking introduced does not in fact lead to a decrease in the elongation at break, as it usually occurs, but is even accompanied by an increase in it.

[0350] In the case of compound 3, the increase in the modulus value lower than that measured for compound 2 could be attributable to the fact that presumably, part of the sulphur destined for vulcanisation was consumed by the norbornene group, resulting overall in a base cross-linking, i.e. net of the reversible cross-linking agent of the invention, lower than the reference.

Dynamic Mechanical Properties

[0351] The dynamic mechanical properties of compounds 1-3 were measured in terms of dynamic elastic modulus (E) and Tan delta (loss factor), in the conditions of low and high deformation described above.

[0352] The pattern of the modulus E and of the Tan delta in the temperature range from 20 C. to 170 C. of the vulcanised samples is shown in FIGS. 4-6.

[0353] From the graph of FIG. 4a it may be observed that the Tan delta (solid line) of the reference compound 1 has a decreasing monotone pattern as the T increases, as expected for conventional elastomeric compounds cross-linked above the Tg. This pattern is associated in the tyre with phenomena of wear, tear resistance and road grip in sports driving which are not completely satisfactory.

[0354] Instead, the graph of FIG. 4b shows that in the case of compound 2 according to the invention, by virtue of the reversible cross-linking of the compound given by the formation of coordinative bonds with zinc, the Tan delta value increases with increasing temperature. This pattern is particularly desirable as it predicts rolling resistance fully comparable to the reference compound at temperatures around 50 C.-70 C. under normal driving conditions but of superior road grip in sport driving conditions, predictable for the greater hysteresis at higher temperatures.

[0355] The graph of FIG. 4c shows that even in the case of the compound 3 according to the invention, the Tan delta value does not have a monotone decreasing pattern as the T increases as for the reference compound (FIG. 4a) but remains almost constant, suggesting properties similar to those described above for compound 2.

[0356] From the superimposed graphs shown in FIG. 5 it is possible to better appreciate the characteristic Tan delta pattern of the compounds according to the invention (2 and 3) with respect to that of the reference compound 1 (without reversible cross-linking agent).

[0357] From the comparison of the graphs shown in FIGS. 6a-6b, relating to samples of reference compound 1 and of the invention 2, the same Tan delta pattern is noted for the compound of the invention as the temperature increases, even with a high deformation measurement procedure, indicative of the triggering of the dissipative mechanism (complexation-decomplexing) in conditions of high temperature and deformation typical of extreme driving, which even leads to double the hysteresis level compared to the reference compound at 170 C., while maintaining for the entire temperature range comparable dynamic modulus values, predictive of an almost constant tread footprint and deformability.

Reversibility of Cross-Linking (Swelling Test)

[0358] This test studied the reversibility of the cross-linking of the vulcanised compounds 1-3 through a swelling experiment in solvent.

[0359] It is known that the equilibrium swelling of a vulcanised compound in a given solvent depends, at constant temperature and pressure, on the lattice density of the compound itself. To demonstrate the hypothesis that inter- and/or intra-molecular bonds due to the cross-linking agents according to the invention are present in the compounds according to the invention, a two-step experiment was carried out: first an equilibrium condition was reached in which the bonds due to the cross-linking agents of the invention were also formed, then a competitive ligand capable of selectively destroying those bonds was added. The increased swelling of the materials after addition proved the correctness of the hypothesis. As shown in FIG. 7, an increase in the swelling value was observed for compounds 2 and 3 (invention) after the addition of tetramethylethylenediamine (TMEDA), competitive binder vs MeBIP, thus demonstrating the reversibility of the cross-linking by complexation: in fact, as shown by the data reported in Table 4 from the addition of the competitive ligand, the swelling increased (increase in weight of the sample of 9.2% and 6.0%) due to the decrease in the extent of cross-linking:

TABLE-US-00004 TABLE 4 swelling of compounds (% weight vs initial weight) 1 2 3 Compositions Ref. Inv. Inv. Reversible cross-linking agent HS-MeBIP Norb-MeBIP (1 mol %) (1 mol %) Salt Zn(OTf).sub.2 Zn(OTf).sub.2 Equilibrium 147.5% 149.1% 148.6% TMEDA added Equilibrium 148.1% 158.3% 154.6% Difference after adding TMEDA +0.6% +9.2% +6.0%

[0360] The counter-proof of the reversible complexation mechanism for the compounds of the invention 2 and 3 was given by the fact that the addition of TMEDA to the reference compound 1, where cross-linking by complexation was not possible, did not produce any increase in the swelling value (FIG. 7), confirming the absence of reversible bonds.